JP2017146620A - Anti-glare film and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-glare film excellent in a balance between haze and clearness and capable of improving anti-glare even when arranged in a high definition display device, highly suppressing glare, and also suppressing character blurs.SOLUTION: A slender projection having a branch structure and total length of 200 μm or more is formed on a surface of an anti-glare layer along with phase separation of a plurality of resin components. The slender projections of one or more per 1 mmexist on the surface of the anti-glare layer. The slender projections may form a co-continuous phase structure. An anti-glare film has a transmission image clearness of 70-100% measured by an image clarity measuring device using an optical comb having width of 0.5 mm, a haze of 10-40% and a total light transmittance of 70-100%.SELECTED DRAWING: None

Description

  The present invention relates to an antiglare film suitable for preventing glare on the display surface of various display devices and reflection of an external light source, and a method for producing the same.

  In order to prevent reflection of an outside scene on a display surface such as a liquid crystal display device or an organic electroluminescence (EL) display device, usually, a mixture of fine particles and a binder resin or a curable resin is applied to a base material and applied to the surface. By forming fine irregularities, regular reflection is prevented and antiglare property is exhibited. However, in a high-definition display device with a small pixel size, the conventional surface unevenness size causes image quality degradation such as screen glare and character blurring. That is, in the case of a high-definition display device, the conventional surface unevenness size is close to the order of the pixel size of high-definition display, and glare occurs due to the lens effect due to the surface unevenness. Further, since the position of the center of gravity of the fine particles cannot be controlled in the coating layer and on the surface structure, the distribution of the transmitted scattered light has a Gaussian distribution centering on the straight transmitted light. Therefore, with the conventional fine particle size, scattering in the vicinity of the linearly transmitted light increases, and the outline of the pixel becomes ambiguous and character blurring occurs. Furthermore, the intensity distribution of the transmitted scattered light depends on the size of the added fine particles, with smaller fine particles, scattering around the straight transmitted light is reduced, glare is reduced, and with larger fine particles, scattering near the straight transmitted light is increased. Glaring occurs.

  In order to solve these problems, attempts have been made to control the uneven shape of the surface by reducing the size of the added fine particles or using fine particles having a sharp particle size distribution. However, in these methods, it is necessary to control the position of the center of gravity of the fine particles in order to prevent glare and blurred characters. Moreover, since the uneven shape on the surface becomes small, it is difficult to achieve sufficient anti-glare properties, and it is disadvantageous from the viewpoint of cost.

  Japanese Patent Application Laid-Open No. 2001-215307 (Patent Document 1) discloses an antiglare layer containing transparent fine particles having an average particle diameter of 15 μm or less in a film having a thickness twice or more the average particle diameter. Among these, an antiglare layer is disclosed in which the transparent fine particles are unevenly distributed on one side in contact with air to form a fine concavo-convex structure. This document also discloses an optical member provided with the antiglare layer on at least one side of a polarizing plate or an elliptical polarizing plate.

  However, in this antiglare layer, since the intensity distribution of transmitted scattered light is controlled by the particle size, glare and character blur on the display surface cannot be effectively prevented.

  Japanese Patent Application Laid-Open No. 2011-13238 (Patent Document 2) discloses an antiglare film in which an antiglare layer is laminated on a translucent substrate as an antiglare film having an uneven surface shape capable of realizing antiglare properties and high contrast. The antiglare layer has a co-continuous structure with a horizontal mesh size of 10 to 150 μm, and the antiglare layer has at least a first phase and a second phase. An antiglare film is disclosed. In this document, a co-continuous structure is formed by aggregating inorganic components in the antiglare layer during film formation. Furthermore, the “co-continuous structure” in this document is defined as a gentle structure in which the slope of the convex portion of the surface irregular shape is small as compared with the conventional antiglare layer.

  However, the bicontinuous structure of this document is manufactured using convection associated with aggregation of inorganic components, and it is difficult to precisely control convection, so the mesh size and mesh thickness (width) Uniformity cannot be achieved. Accordingly, the unevenness of a small size that reduces glare and the unevenness of a large size that emphasizes the orderly glare coexist, and it is essentially impossible to achieve both reduction of glare and antiglare property. Furthermore, when the mesh size is small, glare can be reduced, but sufficient anti-glare properties cannot be exhibited. On the other hand, when the size of the mesh is large, the surface unevenness size is close to the pixel size in order, so that the glare cannot be reduced.

  On the other hand, a method of forming an uneven shape on the surface using spinodal decomposition of an incompatible resin component is also known. Japanese Patent No. 4377578 (Patent Document 3) has an uneven structure on the surface. An anti-glare film comprising an anti-glare layer comprising an at least one polymer and at least one curable resin precursor and having a phase separation structure is disclosed. ing. In this document, in a method for producing a sheet by evaporating a solvent from a solution in which at least one polymer and at least one curable resin precursor are uniformly dissolved, spinodal decomposition is performed under appropriate conditions, and then the precursor is prepared. Is cured, a phase separation structure having regularity in the interphase distance and a surface uneven structure corresponding to the phase structure can be formed, and an antiglare layer having such a regular phase separation structure is formed into a high-definition display device. It is described that glare and character blur on the display surface can be effectively removed when mounted on (specifically, a liquid crystal display device having a resolution of 150 ppi). In particular, in this document, a co-continuous structure is formed as the phase separation proceeds, and when the phase separation further proceeds, a droplet phase structure is formed, a surface uneven structure is formed, and the surface hardness is increased. From the point of view, it is described that a droplet phase structure having at least island-like domains is advantageous, and the formation of island-like domains can form an uneven shape on the surface of the antiglare layer after drying. Furthermore, in this document, the drying temperature for inducing phase separation by spinodal decomposition can be selected from temperatures lower than the boiling point of the solvent (for example, in the range of about 30 to 200 ° C.), preferably 40 to 80 ° C. And is dried at 60 ° C. or 80 ° C. in the examples.

  JP 2008-225195 A (Patent Document 4) discloses a (meth) acrylic resin having a weight average molecular weight of 30,000 to 1,000,000 and a (meth) acrylic resin having a weight molecular weight of 1,000 to 100,000 and having a polymerizable group. And an anti-glare film composed of a cured product with a polyfunctional (meth) acrylate, wherein the string-like convex portions having an average width of 0.1 to 30 μm are dispersed and formed in a random direction on the surface, And the anti-glare film | membrane whose area ratio of the said string-like convex part is 50% or less with respect to the whole surface is disclosed. This document also describes that a droplet phase structure having at least island-like domains is advantageous, and the formation of island-like domains can form an uneven shape on the surface of the antiglare layer after drying. Furthermore, in this document, in order to induce convection and phase separation, the temperature is lower than the boiling point of the solvent (for example, 30 to 200 ° C., particularly preferably 40 to 80 ° C.) after standing at room temperature or room temperature for a certain period of time. In the examples, after standing at room temperature for 10 seconds, it is dried in an explosion-proof oven at 60 ° C. or 70 ° C. and a wind speed of 3 m / min.

  However, in the antiglare films of Patent Documents 3 and 4, the antiglare property is maintained in a high-definition display device (for example, a liquid crystal display device or an organic EL display device having a resolution of 200 ppi or higher) having a resolution higher than 150 ppi. The glare cannot be reduced. In particular, as the distance between the display surface and the anti-glare layer increases, glare tends to occur. However, in the protection or protection film of the display device (the film that the user attaches to the display surface after purchase), Due to the presence of the adhesive layer, the distance from the display surface is large, and it is difficult to suppress glare. Furthermore, among the high-definition display devices, the organic EL panel has high pixel emission intensity, and thus easily causes glare, and it is difficult to achieve both anti-glare properties and suppression of character blur. Antiglare film cannot be compatible.

JP 2001-215307 A (Claims) JP 2011-13238 A (claims, paragraphs [0012] [0035]) Japanese Patent No. 4377578 (Claim 1, paragraphs [0058] [0059] [0071] [0083], Examples) JP 2008-225195 A (claims, paragraphs [0068] [0069] [0074] [0075], Examples)

  Therefore, the object of the present invention is to provide an excellent balance between haze and sharpness, and even when disposed in a high-definition display device (for example, a liquid crystal display device having a resolution of 200 ppi or higher, an organic EL display device, etc.). An object of the present invention is to provide an antiglare film that can improve dazzling properties, can suppress glare to a high degree, and can suppress character blurring, and a method for producing the same.

  Another object of the present invention is to prevent anti-glare and anti-glare properties, and to improve scratch resistance even when arranged away from the display surface of a high-definition display device such as an organic EL panel. It is in providing a dazzling film and its manufacturing method.

  The present inventors first examined a mechanism by which a conventional antiglare film using spinodal decomposition of an incompatible resin component cannot achieve both antiglare property and glare resistance in a high-definition display device. The conventional concavo-convex structure by phase separation has a structure in which droplet-like structures are arranged relatively periodically as shown in FIG. Phase separation occurs when a mixture of resins that are thermodynamically stable due to uniform dissolution in the coating solution becomes thermodynamically unstable as the solvent evaporates, causing spinodal decomposition. It is a phenomenon. Since the entire system becomes thermodynamically unstable at the same time and homogeneous phase separation proceeds in the coating film surface, the surface irregularity shape of a relatively periodic and uniform size is formed. . However, if the size of the surface irregularity is reduced to such an extent that the glare can be suppressed with respect to a pixel size corresponding to a resolution of 200 ppi or more, the antiglare property is lowered, and external light is reflected on the display surface and the image quality is impaired. End up. On the other hand, when the inclination angle of the convex shape is increased in order to improve the antiglare property, haze increases and character blurring occurs.

  In general, glare is considered to occur due to the lens effect when the size of the concavo-convex structure is orderly close to the pixel size. As a presumption, when the concavo-convex shape exists across the pixels, the transmitted light of each pixel is refracted in different directions depending on the concavo-convex shape, and the color and brightness that should originally reach the evaluator's eyes as RGB mixed colors are It is thought that the phenomenon which is felt by randomly changing according to the pitch and inclination of the concavo-convex structure is recognized as glare. When the concavo-convex structure is sufficiently smaller than the pixel, the concavo-convex straddling the pixel is present, but since the ratio is small and the refraction is small, the glare is hardly felt. On the other hand, when the concavo-convex structure is sufficiently larger than the pixel, if the inclination of the concavo-convex shape is large, the transmitted light is largely refracted to produce a lens effect. However, the smaller the inclination is, the less the refraction of the transmitted light is and it is difficult to feel glare. Although it is easy to understand when considering an extreme case, it can be predicted that if the tilt angle is as close to zero as possible, it becomes almost flat and the glare is eliminated.

  Therefore, the present inventors have found that the conventional anti-glare film has a droplet phase structure, and thus it is easy to generate glare, and pay attention to a bicontinuous phase structure (bicontinuous structure or bicontinuous phase separation structure). did. In other words, in a phase separation structure including a co-continuous phase structure, adjustment is necessary depending on the pixel size, but by adjusting the width of the convex portion forming the co-continuous phase structure to a width sufficiently smaller than the pixel, the width direction is glaring. You will be exempt from the factors that cause On the other hand, in the length (sustained length) direction of the convex portion, there is no inclination in principle other than the end portion, so that glare is hardly generated. In particular, not only in the bicontinuous phase structure, but also in the droplet phase structure, when the length of the island-like domain is large, the ratio of the end portion is small, so that the glare is hardly generated. In addition, although the size in the width direction is small, the co-continuous phase structure and the island-like domain portion having a large length are greatly spread in the film surface direction, so that it is easy to ensure antiglare properties. Furthermore, since the co-continuous phase structure is a structure having essentially few inclined portions, there are few factors that scatter light, and the haze is smaller than that of a droplet-like surface uneven structure having a size similar to the width direction. Because it is low, character blurring is difficult to occur.

  Based on such knowledge, the present inventors have intensively studied to achieve the above problems, and as a result, the surface of the antiglare layer has a branched structure accompanying phase separation of a plurality of resin components, and By forming dense projections with a total length of 100 μm or more densely, the balance between haze and sharpness is excellent, and high-definition display devices (for example, liquid crystal display devices having a resolution of 200 ppi or more, organic EL The present invention has been completed by finding that the antiglare property can be improved, the glare can be suppressed to a high degree, and the character blur can be suppressed even if it is disposed on a display device.

That is, the anti-glare film of the present invention is an anti-glare film including an anti-glare layer having on its surface an elongated convex portion formed in accordance with phase separation of a plurality of resin components, and the elongated convex portion. However, it has a branched structure and has a total length of 100 μm or more, and one or more elongated protrusions per 1 mm ^{2 on} the surface of the antiglare layer. The elongated protrusions may form a co-continuous phase structure, and the average mesh diameter of the co-continuous phase structure may be 1 to 70 μm. On the surface of the antiglare layer, the length ratio of the elongated convex portion having a branched structure to other convex portions may be about the former / the latter = 100/0 to 50/50. The antiglare film of the present invention has a transmitted image sharpness of 70 to 100%, a haze of 10 to 40%, and a total light transmittance of 70 to 100% as measured by a image clarity measuring instrument using an optical comb having a width of 0.5 mm. You may do it. The plurality of resin components include a plurality of polymers selected from styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, aliphatic organic acid cellulose esters, and aromatic organic acid cellulose esters. At least one cure selected from epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, silicone (meth) acrylates, and polyfunctional monomers having at least two polymerizable unsaturated bonds And at least two components of the polymer are phase-separated by spinodal decomposition from the liquid phase, and the curable resin precursor may be cured. The said curable resin precursor may contain the curable resin precursor whose viscosity (25 degreeC) based on JISZ8803 is 3000 mPa * s or less. The anti-glare film of the present invention may be an anti-glare film capable of suppressing glare even when the anti-glare layer is separated from the display surface by 0.05 mm or more when disposed in a display device having a resolution of 200 ppi. The display device may be an organic EL panel. The antiglare film of the present invention further includes a transparent film, and the antiglare layer may be formed on one surface of the transparent film. In this antiglare film, an adhesive layer may be formed on the other surface of the transparent film. The antiglare film of the present invention may be a protective or protect film disposed on the outermost surface of the display device.

  The present invention also includes a method for producing the antiglare film, which includes a drying step of applying a solution containing a plurality of resin components and forming a phase separation structure by spinodal decomposition accompanying evaporation of the solvent. In the drying step, heating may be performed at a temperature exceeding 80 ° C.

  In the present specification, “(meth) acryl”, “(meth) acrylate” and “(meth) acrylic acid” mean “acryl or methacryl”, “acrylate or methacrylate” and “acryloyl or methacryloyl”, respectively. To do.

  In the present invention, on the surface of the antiglare layer, along with the phase separation of a plurality of resin components, there are branched structures, and elongated protrusions having a total length of 100 μm or more are densely formed. Excellent balance between haze and sharpness, anti-glare property can be improved even when placed in a high-definition display device (for example, a liquid crystal display device having a resolution of 200 ppi or higher, an organic EL display device, etc.) It can be highly controlled and character blur can be suppressed. Furthermore, even if it arrange | positions away with respect to the display surface of high-definition display apparatuses, such as an organic electroluminescent panel, anti-glare property and glare-proof property can be made compatible, and abrasion resistance can also be improved. Therefore, even if it uses as a protective film of high-definition display apparatuses, such as an organic EL panel, the said characteristic can be made compatible.

FIG. 1 is a laser reflection micrograph of the surface of an antiglare layer of a conventional antiglare film (antiglare film obtained in Comparative Example 2) utilizing spinodal decomposition of an incompatible resin component. 2 is a laser reflection micrograph of the antiglare layer surface of the antiglare film obtained in Example 1. FIG. 3 is a laser reflection micrograph of the antiglare layer surface of the antiglare film obtained in Example 2. FIG.

[Anti-glare layer]
The anti-glare film of the present invention includes an anti-glare layer, and this anti-glare layer has a long (or long) convex portion formed on the surface as a result of phase separation of a plurality of resin components. The anti-glare property can be exhibited by the surface uneven structure formed by the elongated protrusions. In particular, in the present invention, the elongated convex portion has a branched structure and a total length of 100 μm or more, and forms a co-continuous phase structure in a dense state on the surface of the antiglare layer. Therefore, it is excellent in the balance between haze and sharpness, and even when arranged in a high-definition display device, glare can be suppressed to a high degree and character blurring can be suppressed without impairing the antiglare property.

(Elongated convex part)
The elongated protrusions are formed by phase separation of a plurality of resin components by a method described later, and the elongated (string-like or linear) protrusions are formed in a substantially mesh shape on the surface of the antiglare layer. ing. Therefore, the surface of the antiglare layer has a two-dimensional network-like network structure (as if it is a mask melon skin-like mesh pattern), that is, a plurality of irregular loops (for example, continuous loops, or part of them) It can be observed as forming a loop lacking.

Specifically, the antiglare layer has a branched structure and has one or more elongated convex portions per 1 mm ² on the surface having a total length of 100 μm or more (preferably 200 μm or more, more preferably 500 μm or more). It only has to be. In addition, although the said elongate convex part may have multiple, when the whole surface of a glare-proof layer is a co-continuous phase structure, the length of the said elongate convex part which has a branched structure becomes infinite length The number that exists in any region is 1. The “total length” of the elongated protrusions means the total length of the lengths of the branched branches in the continuous elongated protrusions.

  The branched structure of the elongated protrusions may have at least one branch, but it is preferable that the elongated protrusions branch in a mesh shape to form a co-continuous phase structure. As used herein, the term “co-continuous phase structure” refers to a continuous structure (or network structure) formed by connecting droplet-shaped convex structures, which are generated in the process of manufacture, in the process of phase separation. means.

  In addition, it is not necessary that all the long convex portions have a co-continuous phase structure, and the original droplet-like convex structure (that is, a long convex portion having no branch, a substantially circular convex portion, (Non-elongated convex portions such as elliptical convex portions) may be included. In the present invention, by having such a long convex portion, the proportion of the end portion is reduced as compared to the island-shaped convex portion of the droplet phase structure (or sea-island structure), and glare and character blur are reduced. Can be suppressed. Furthermore, in the bicontinuous phase structure formed along with the phase separation of the resin component, since the end portion has a small inclination, glare and character blur can be suppressed.

  On the surface of the anti-glare layer, the length ratio between the elongated convex part having a branched structure and the other convex part (original liquid droplet-like convex part) is, for example, the former / the latter = 100/0 The range can be selected from the range of about 10/90, for example, 100/0 to 30/70, preferably 100/0 to 50/50, more preferably 100/0 to 70/30 (particularly 100/0 to 90/10). About 100% (for example, the entire surface is a co-continuous phase structure) is particularly preferable. If the length ratio is small and the ratio of the elongated protrusions having a branched structure is too small, the ratio of the droplet phase structure increases. Therefore, if anti-glare properties are improved, glare and text blur are likely to occur. .

  In the co-continuous phase structure formed by elongated protrusions, the meshes having the same diameter are usually arranged in an irregular shape. The average diameter of each network of the bicontinuous phase structure (when each network of the bicontinuous phase structure is an anisotropic shape such as an elliptical shape or a rectangular shape) is, for example, 1 to 70 μm (for example, 1-40 μm), preferably 2-50 μm (for example, 3-30 μm), more preferably about 5-20 μm (especially 10-20 μm). If the mesh diameter is too large, glare and character blur are likely to occur, and if it is too small, the anti-glare property tends to decrease.

  The shape of each elongated protrusion (two-dimensional shape of the antiglare layer surface) is usually a string having a curved portion partially or entirely, and the average width of the elongated protrusion is 0.1 to It is 30 μm, and it may be selected from the above range according to the pixel of the display device and adjusted to a small width capable of suppressing glare. For example, 0.1 to 20 μm, preferably 0.1 to 15 μm, more preferably Is about 0.1 to 10 μm (particularly 0.1 to 5 μm). When the width is too large, glare and character blur are likely to occur, and when it is too small, the antiglare property is lowered. In addition, in order to change the surface shape in the direction of optimizing the interfacial tension when connecting the droplet-like projections, the width of the long and narrow projections of the co-continuous phase structure formed by connecting the droplet-like projections is It does not necessarily have to be the same as the size of the original droplet-shaped convex portion.

  The average height of the elongated protrusions is, for example, about 0.05 to 10 μm, preferably 0.07 to 5 μm, and more preferably about 0.09 to 3 μm (particularly 0.1 to 2 μm). The inclination angle of the elongated protrusion is, for example, 10 ° or less, preferably 0.5 to 5 °, more preferably about 1 to 3 °. If the height of the convex portion is high and the inclination becomes large, glare and character blur are likely to occur.

  The area ratio of all the convex portions on the surface of the antiglare layer is, for example, about 10 to 100%, preferably 30 to 100%, more preferably about 50 to 100% (particularly 70 to 100%) with respect to the entire surface. is there. If the area between the elongated protrusions is too small, the antiglare property tends to decrease, and if it is too large, glare and character blur are likely to occur.

  In the present specification, the size or shape (such as the presence or absence of branching) and the area of the elongated protrusion can be measured or evaluated based on a two-dimensional shape observed with a micrograph. Moreover, an average value is an average value of the values measured at arbitrary 10 or more locations. Further, the length ratio between the elongated convex part and the other convex part can be obtained by measuring each length in an area of 1 mm2. In particular, since the elongated convex portions (or bicontinuous phase structure) in the present invention form a continuous structure by connecting the droplet phase structure, the shape of each elongated convex portion is a convex portion in microscopic observation. Can be identified based on the ridge-like (ridgeline) portion where the vertices are connected. Furthermore, in the present specification, the length of the elongated convex portion can be measured as the length of the ridge portion, and the mesh diameter of the co-continuous phase structure can be obtained based on the ridge portion. The details can be measured by the method described in Examples described later. The inclination angle of the elongated convex portion can be measured with a surface roughness meter (for example, “Surfcom” manufactured by Toyo Seimitsu Co., Ltd.) in accordance with JIS standards.

(Resin component)
The antiglare layer includes a plurality of phase-separable resin components, and the phase separation structure of the antiglare layer is formed by spinodal decomposition (wet spinodal decomposition) from the liquid phase. The resin component only needs to contain a phase-separable resin component, but includes a polymer component and a curable resin precursor from the viewpoint that the above-described elongated protrusions can be formed and the scratch resistance can be improved. Is preferred.

(Polymer component)
As the polymer component, a thermoplastic resin is usually used. Thermoplastic resins include styrene resins, (meth) acrylic resins, organic acid vinyl ester resins, vinyl ether resins, halogen-containing resins, olefin resins (including alicyclic olefin resins), polycarbonate resins, Polyester resin, polyamide resin, thermoplastic polyurethane resin, polysulfone resin (polyethersulfone, polysulfone, etc.), polyphenylene ether resin (2,6-xylenol polymer, etc.), cellulose derivatives (cellulose esters, cellulose carbamate) , Cellulose ethers, etc.), silicone resins (polydimethylsiloxane, polymethylphenylsiloxane, etc.), rubbers or elastomers (diene rubbers such as polybutadiene, polyisoprene, styrene-butadiene copolymers) Acrylonitrile - butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber, etc.), and others. These thermoplastic resins can be used alone or in combination of two or more.

  Styrene resins include styrene monomers alone or copolymers (polystyrene, styrene-α-methylstyrene copolymer, styrene-vinyltoluene copolymer, etc.), styrene monomers and other polymerizable properties. Copolymers with monomers [(meth) acrylic monomers, maleic anhydride, maleimide monomers, dienes, etc.] are included. Examples of the styrene-based copolymer include a styrene-acrylonitrile copolymer (AS resin), a copolymer of styrene and a (meth) acrylic monomer [styrene-methyl methacrylate copolymer, styrene-methacrylic acid. Methyl- (meth) acrylic acid ester copolymer, styrene-methyl methacrylate- (meth) acrylic acid copolymer, etc.], styrene-maleic anhydride copolymer and the like. Preferred styrenic resins include polystyrene, copolymers of styrene and (meth) acrylic monomers [copolymers based on styrene and methyl methacrylate such as styrene-methyl methacrylate copolymer], AS resin, styrene-butadiene copolymer and the like are included.

As the (meth) acrylic resin, a (meth) acrylic monomer alone or a copolymer, a copolymer of a (meth) acrylic monomer and a copolymerizable monomer, or the like can be used. Examples of (meth) acrylic monomers include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, ( (Meth) acrylic acid isobutyl, (meth) acrylic acid hexyl, (meth) acrylic acid octyl, (meth) acrylic acid 2-ethylhexyl (meth) acrylic acid C _1-10 alkyl; (meth) acrylic acid phenyl ( (Meth) acrylic acid aryl; hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate; glycidyl (meth) acrylate; N, N-dialkylaminoalkyl (meth) acrylate; (meth) acrylonitrile The alicyclic hydrocarbon group such as tricyclodecane The (meth) acrylate etc. which have can be illustrated. Examples of the copolymerizable monomer include the styrene monomer, vinyl ester monomer, maleic anhydride, maleic acid, and fumaric acid. These monomers can be used alone or in combination of two or more.

Examples of the (meth) acrylic resin include poly (meth) acrylic acid esters such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer Examples thereof include methyl methacrylate, acrylic acid ester- (meth) acrylic acid copolymer, and (meth) acrylic acid ester-styrene copolymer (MS resin and the like). Preferable (meth) acrylic resins include poly (meth) acrylic acid C _1-6 alkyl such as poly (meth) methyl acrylate, particularly methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100%). And a methyl methacrylate-based resin.

  Organic acid vinyl ester resins include vinyl ester monomers alone or copolymers (polyvinyl acetate, polyvinyl propionate, etc.), and vinyl ester monomers and copolymerizable monomers. Examples thereof include a copolymer (ethylene-vinyl acetate copolymer, vinyl acetate-vinyl chloride copolymer, vinyl acetate- (meth) acrylic ester copolymer, etc.) or a derivative thereof. Examples of the vinyl ester resin derivative include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetal resin, and the like.

Examples of vinyl ether resins include vinyl C _1-10 alkyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and vinyl t-butyl ether, or copolymers, and vinyl C _1-10 alkyl ethers and copolymers. And a copolymer with a monomer (such as a vinyl alkyl ether-maleic anhydride copolymer).

  Examples of the halogen-containing resin include polyvinyl chloride, polyvinylidene fluoride, vinyl chloride-vinyl acetate copolymer, vinyl chloride- (meth) acrylate ester copolymer, vinylidene chloride- (meth) acrylate ester copolymer, and the like. Can be mentioned.

  Examples of the olefin resin include homopolymers of olefins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meta ) Copolymers such as acrylic acid ester copolymers. As the alicyclic olefin-based resin, a cyclic olefin (norbornene, dicyclopentadiene, etc.) alone or a copolymer (for example, a polymer having an alicyclic hydrocarbon group such as sterically rigid tricyclodecane, etc.) And a copolymer of the cyclic olefin and a copolymerizable monomer (such as an ethylene-norbornene copolymer and a propylene-norbornene copolymer). The alicyclic olefin-based resin can be obtained, for example, under the trade name “ARTON” or the trade name “ZEONEX”.

  Polycarbonate resins include aromatic polycarbonates based on bisphenols (such as bisphenol A) and aliphatic polycarbonates such as diethylene glycol bisallyl carbonate.

Polyester resins include aromatic polyesters using aromatic dicarboxylic acids such as terephthalic acid [homopolyesters such as poly C _2-4 alkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate and poly C _2-4 alkylene naphthalates, Examples thereof include a copolyester containing a C _2-4 alkylene arylate unit (C _2-4 alkylene terephthalate and / or C _2-4 alkylene naphthalate unit) as a main component (for example, 50% by weight or more). The copolyesters, poly _{C 2-4} among constituent units of alkylene _{arylate, C 2-4} part of the alkylene glycol, polyoxy _{C 2-4} alkylene _{glycols, C 6-10} alkylene glycol, alicyclic diols (cyclohexane Dimethanol, hydrogenated bisphenol A and the like, diols having aromatic rings (9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene having a fluorenone side chain, bisphenol A, bisphenol A-alkylene oxide adducts, etc. ) Substituted copolyesters, copolyesters partially substituted with asymmetric aromatic dicarboxylic acids such as phthalic acid and isophthalic acid, and aliphatic C _6-12 dicarboxylic acids such as adipic acid It is. Polyester resins also include polyarylate resins, aliphatic polyesters using aliphatic dicarboxylic acids such as adipic acid, and homopolymers or copolymers of lactones such as ε-caprolactone. A preferred polyester resin is usually amorphous, such as an amorphous copolyester (for example, C _2-4 alkylene arylate copolyester).

  Examples of polyamide resins include aliphatic polyamides such as nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11 and nylon 12, dicarboxylic acids (for example, terephthalic acid, isophthalic acid, adipic acid, etc.) and diamines ( Examples thereof include polyamides obtained from hexamethylenediamine and metaxylylenediamine). The polyamide-based resin may be a lactam homopolymer or copolymer such as ε-caprolactam, and is not limited to homopolyamide but may be copolyamide.

Among cellulose derivatives, cellulose esters include, for example, aliphatic organic acid esters (cellulose acetate such as cellulose diacetate and cellulose triacetate; cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate). C _1-6 organic acid esters, etc.), aromatic organic acid esters (C _7-12 aromatic carboxylic acid esters such as cellulose phthalate and cellulose benzoate), and inorganic acid esters (eg, cellulose phosphate, cellulose sulfate, etc.). Examples thereof include mixed acid esters such as acetic acid and cellulose nitrate ester. Cellulose derivatives include cellulose carbamates (eg, cellulose phenyl carbamate), cellulose ethers (eg, cyanoethyl cellulose; hydroxy C _2-4 alkyl cellulose such as hydroxyethyl cellulose, hydroxypropyl cellulose; C _{1- 1} such as methyl cellulose, ethyl cellulose, etc. ₆ alkylcellulose; carboxymethylcellulose or a salt thereof, benzylcellulose, acetylalkylcellulose, etc.).

  Preferred thermoplastic resins include, for example, styrene resins, (meth) acrylic resins, vinyl acetate resins, vinyl ether resins, halogen-containing resins, alicyclic olefin resins, polycarbonate resins, polyester resins, and polyamide resins. Examples thereof include resins, cellulose derivatives, silicone resins, and rubbers or elastomers. As the resin, a resin that is amorphous and is soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds) is usually used. In particular, resins with high moldability or film formability, transparency and weather resistance, such as styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) Etc. are preferable.

As the polymer component, a polymer having a functional group involved in the curing reaction (or a functional group capable of reacting with the curable compound) can also be used. The polymer may have a functional group in the main chain or a side chain. The functional group may be introduced into the main chain by copolymerization or cocondensation, but is usually introduced into the side chain. Such functional groups include condensable groups and reactive groups (for example, hydroxyl groups, acid anhydride groups, carboxyl groups, amino groups or imino groups, epoxy groups, glycidyl groups, isocyanate groups, etc.), polymerizable groups ( For example, C _2-6 alkenyl group such as vinyl, propenyl, isopropenyl group, butenyl and allyl, C _2-6 alkynyl group such as ethynyl, propynyl and butynyl, C _2-6 alkenylidene group such as vinylidene, or polymerization thereof A group having a functional group (such as a (meth) acryloyl group). Of these functional groups, a polymerizable group is preferable.

  As a method for introducing a polymerizable group into a side chain, for example, a thermoplastic resin having a functional group such as a reactive group or a condensable group is reacted with a polymerizable compound having a reactive group with the functional group. The method can be used.

  Examples of the thermoplastic resin having a functional group include a thermoplastic resin having a carboxyl group or its acid anhydride group (for example, (meth) acrylic resin, polyester resin, polyamide resin, etc.), and a thermoplastic resin having a hydroxyl group. (For example, (meth) acrylic resins, polyurethane resins, cellulose derivatives, polyamide resins, etc.), thermoplastic resins having amino groups (for example, polyamide resins), thermoplastic resins having epoxy groups (for example, epoxy) Examples thereof include (meth) acrylic resins and polyester resins having a group). Moreover, the resin which introduce | transduced the said functional group into copolymerization or graft polymerization to thermoplastic resins, such as a styrene resin, an olefin resin, and an alicyclic olefin resin, may be sufficient.

  As the polymerizable compound, in the case of a thermoplastic resin having a carboxyl group or its acid anhydride group, a polymerizable compound having an epoxy group, a hydroxyl group, an amino group, an isocyanate group, or the like can be used. In the case of a thermoplastic resin having a hydroxyl group, a polymerizable compound having a carboxyl group or its acid anhydride group or an isocyanate group can be used. In the case of a thermoplastic resin having an amino group, a polymerizable compound having a carboxyl or its acid anhydride group, an epoxy group, an isocyanate group, or the like can be used. In the case of a thermoplastic resin having an epoxy group, a polymerizable compound having a carboxyl group or an acid anhydride group or an amino group thereof can be used.

Among the polymerizable compounds, examples of the polymerizable compound having an epoxy group include epoxycyclo C _5-8 alkenyl (meth) acrylate such as epoxycyclohexenyl (meth) acrylate, glycidyl (meth) acrylate, allyl glycidyl ether, and the like. Can be illustrated. Examples of the compound having a hydroxyl group include hydroxy C _1-4 alkyl (meth) acrylate such as hydroxypropyl (meth) acrylate, C _2-6 alkylene glycol (meth) acrylate such as ethylene glycol mono (meth) acrylate, and the like. It can be illustrated. Examples of the polymerizable compound having an amino group include amino _C1-4 alkyl (meth) acrylate such as aminoethyl (meth) acrylate, C _3-6 alkenylamine such as allylamine, 4-aminostyrene, diaminostyrene, and the like. Examples include aminostyrenes. Examples of the polymerizable compound having an isocyanate group include (poly) urethane (meth) acrylate and vinyl isocyanate. Examples of the polymerizable compound having a carboxyl group or an acid anhydride group thereof include unsaturated carboxylic acids such as (meth) acrylic acid and maleic anhydride, or anhydrides thereof.

  As a typical example, a thermoplastic resin having a carboxyl group or its acid anhydride group and an epoxy group-containing compound, particularly a (meth) acrylic resin ((meth) acrylic acid- (meth) acrylic acid ester copolymer, etc.) ) And an epoxy group-containing (meth) acrylate (such as epoxycycloalkenyl (meth) acrylate and glycidyl (meth) acrylate). Specifically, a polymer in which a polymerizable unsaturated group is introduced into a part of the carboxyl group of the (meth) acrylic resin, for example, one of the carboxyl groups of the (meth) acrylic acid- (meth) acrylic acid ester copolymer. A (meth) acrylic polymer in which the epoxy group of 3,4-epoxycyclohexenylmethyl acrylate is reacted with the part to introduce a photopolymerizable unsaturated group into the side chain can be used.

  The introduction amount of the functional group (particularly polymerizable group) involved in the curing reaction for the thermoplastic resin is 0.001 to 10 mol, preferably 0.01 to 5 mol, more preferably 0 with respect to 1 kg of the thermoplastic resin. About 0.02 to 3 moles.

These polymers can be used in appropriate combinations. That is, the polymer may be composed of a plurality of polymers. The plurality of polymers may be phase separable by liquid phase spinodal decomposition. The plurality of polymers may be incompatible with each other. When combining a plurality of polymers, the combination of the first resin and the second resin is not particularly limited, but suitable as a plurality of polymers incompatible with each other near the processing temperature, for example, two polymers incompatible with each other Can be used in combination. For example, when the first resin is a styrene resin (polystyrene, styrene-acrylonitrile copolymer, etc.), the second resin is a cellulose derivative (for example, cellulose esters such as cellulose acetate propionate), (meta ) Acrylic resins (such as polymethyl methacrylate), alicyclic olefin resins (such as polymers having norbornene as a monomer), polycarbonate resins, polyester resins (the poly C _2-4 alkylene arylate copolyester) Etc.). For example, when the first polymer is a cellulose derivative (for example, cellulose esters such as cellulose acetate propionate), the second polymer is a styrene resin (polystyrene, styrene-acrylonitrile copolymer, etc.), (Meth) acrylic resins, alicyclic olefin resins (such as polymers containing norbornene as monomers), polycarbonate resins, polyester resins (such as the poly C _2-4 alkylene arylate copolyesters). May be. In a combination of a plurality of resins, at least cellulose esters (for example, cellulose C _2-4 alkyl carboxylic acid esters such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate) may be used.

  In addition, the phase separation structure produced | generated by spinodal decomposition | disassembly is finally hardened | cured with actinic light (an ultraviolet ray, an electron beam, etc.), a heat | fever, etc., and forms cured resin. Therefore, scratch resistance can be imparted to the antiglare layer, and durability can be improved.

  From the viewpoint of scratch resistance after curing, at least one of a plurality of polymers, for example, one of the incompatible polymers (when combining the first resin and the second resin, Both polymers are preferably polymers having functional groups in the side chain capable of reacting with the curable resin precursor.

  The ratio (weight ratio) between the first polymer and the second polymer is, for example, the former / the latter = 1/99 to 99/1, preferably 5/95 to 95/5, more preferably 10/90 to 90. Can be selected from the range of about / 10, and is usually about 20/80 to 80/20, particularly about 30/70 to 70/30.

  In addition, as a polymer for forming a phase-separated structure, the said thermoplastic resin and another polymer other than the said two incompatible polymers may be contained.

  The glass transition temperature of the polymer can be selected from the range of, for example, −100 ° C. to 250 ° C., preferably −50 ° C. to 230 ° C., more preferably about 0 to 200 ° C. (for example, about 50 to 180 ° C.). From the viewpoint of surface hardness, the glass transition temperature is advantageously 50 ° C. or higher (for example, about 70 to 200 ° C.), preferably 100 ° C. or higher (for example, about 100 to 170 ° C.). The weight average molecular weight of a polymer can be selected from the range of about 1,000,000 or less, preferably about 1,000 to 500,000, for example.

(Curable resin precursor)
The curable resin precursor is a compound having a functional group that reacts with heat or active energy rays (such as ultraviolet rays or electron beams), and is cured or crosslinked with heat or active energy rays or the like (particularly cured or crosslinked). Various curable compounds capable of forming (resin) can be used. Examples of the resin precursor include thermosetting compounds or resins [low molecular weight compounds having an epoxy group, a polymerizable group, an isocyanate group, an alkoxysilyl group, a silanol group, etc. (for example, epoxy resins, unsaturated polyester resins) , Urethane resins, silicone resins, etc.)], photocurable compounds curable with actinic rays (such as ultraviolet rays) (photocurable monomers, ultraviolet curable compounds such as oligomers), etc. May be an EB (electron beam) curable compound. Note that a photocurable compound such as a photocurable monomer, an oligomer, or a photocurable resin that may have a low molecular weight may be simply referred to as a “photocurable resin”.

  Photocurable compounds include, for example, monomers and oligomers (or resins, particularly low molecular weight resins). Examples of monomers include monofunctional monomers [(meth) acrylic acid esters, etc. (Meth) acrylic monomer, vinyl monomer such as vinylpyrrolidone, (meth) acrylate having a bridged cyclic hydrocarbon group such as isobornyl (meth) acrylate, adamantyl (meth) acrylate, etc.], at least two Polyfunctional monomer having a polymerizable unsaturated bond [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di Alkylene glycol di (meth) acrylate such as (meth) acrylate; (Poly) oxyalkylene glycol di (meth) acrylate such as lenglycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyoxytetramethylene glycol di (meth) acrylate; tricyclodecane dimethanol di (meth) Di (meth) acrylates having a bridged cyclic hydrocarbon group such as acrylate and adamantane di (meth) acrylate; trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, And polyfunctional monomers having about 3 to 6 polymerizable unsaturated bonds such as pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate].

  Examples of oligomers or resins include (meth) acrylates of bisphenol A-alkylene oxide adducts, epoxy (meth) acrylates (bisphenol A type epoxy (meth) acrylates, novolac type epoxy (meth) acrylates, etc.), polyester (meth) acrylates ( For example, aliphatic polyester type (meth) acrylate, aromatic polyester type (meth) acrylate, etc.), (poly) urethane (meth) acrylate (polyester type urethane (meth) acrylate, polyether type urethane (meth) acrylate, etc.), Examples thereof include silicone (meth) acrylate. These photocurable compounds can be used alone or in combination of two or more.

  Preferred curable resin precursors are photocurable compounds that can be cured in a short time, for example, ultraviolet curable compounds (monomers, oligomers, resins that may be low molecular weight, etc.), and EB curable compounds. In particular, a practically advantageous resin precursor is an ultraviolet curable resin. Further, in order to improve resistance such as scratch resistance, the photocurable resin is a compound having 2 or more (preferably about 2 to 15, more preferably about 4 to 10) polymerizable unsaturated bonds in the molecule. Is preferred. Specifically, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, silicone (meth) acrylate, and a polyfunctional monomer having at least two polymerizable unsaturated bonds are preferable.

  The molecular weight of the curable resin precursor is about 5000 or less, preferably about 2000 or less, more preferably about 1000 or less in consideration of compatibility with the polymer.

  The viscosity of the curable resin precursor (viscosity at 25 ° C. according to JIS Z8803) can be selected from a range of about 100 to 10000 mPa · s (particularly 500 to 8000 mPa · s). In particular, the curable resin precursor preferably includes a low-viscosity curable resin precursor having a viscosity of at least 3000 mPa · s from the viewpoint of easily forming the elongated convex portion. The viscosity of the low-viscosity curable resin precursor (viscosity at 25 ° C. according to JIS Z8803) is, for example, 100 to 3000 mPa · s, preferably 300 to 2800 mPa · s, more preferably 500 to 2500 mPa · s (particularly 1000 to 1000 mPa · s). 2300 mPa · s). If the viscosity of the low-viscosity curable resin precursor is too high, it becomes difficult to form the elongated protrusions. The mechanism by which the elongated protrusions are easily formed by including a low-viscosity curable resin precursor is not clear, but the low-viscosity curable resin precursor is melt flowability of the coating liquid in the drying process, particularly the phase. By improving the degree of freedom of the thermoplastic resin to be separated, it can be estimated that the spinodal decomposition is promoted and proceeds from a droplet phase structure to a co-continuous phase structure.

  The proportion of the low-viscosity curable resin precursor can be selected from the range of about 1 to 50% by weight, for example, 3 to 40% by weight, preferably 5 to 35% by weight, and more preferably 10%, based on the entire resin component. It is about -30 wt% (especially 15-25 wt%). If the proportion of the low-viscosity resin precursor is too large, the formation of the initial unevenness accompanying the phase separation of spinodal decomposition is suppressed, and the chance of connecting the convex portions by melting decreases, so it becomes difficult to form long and thin convex portions. If the amount is too small, the melt fluidity of the coating solution decreases, and it becomes difficult to form the elongated protrusions.

  The curable resin precursor may contain a curing agent depending on the type. For example, the thermosetting resin may contain a curing agent such as amines and polyvalent carboxylic acids, and the photocurable resin may contain a photopolymerization initiator. Examples of the photopolymerization initiator include conventional components such as acetophenones or propiophenones, benzyls, benzoins, benzophenones, thioxanthones, acylphosphine oxides, and the like. The content of the curing agent such as a photocuring agent is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight (100 parts by weight based on 100 parts by weight of the curable resin precursor. In particular, it is about 1 to 5 parts by weight, and may be about 3 to 8 parts by weight.

  Furthermore, the curable resin precursor may contain a curing accelerator. For example, the photocurable resin may contain a photocuring accelerator, for example, a tertiary amine (such as a dialkylaminobenzoic acid ester), a phosphine photopolymerization accelerator, and the like.

  Of the at least one polymer and the at least one curable resin precursor, at least two components are used in combination that phase separate from each other near the processing temperature. Examples of combinations for phase separation include (a) a combination in which a plurality of polymers are incompatible with each other, (b) a combination in which a polymer and a curable resin precursor are incompatible and phase separated, c) A combination of a plurality of curable resin precursors incompatible with each other and phase separated. Of these combinations, (a) a combination of a plurality of polymers, or (b) a combination of a polymer and a curable resin precursor, and (a) a combination of a plurality of polymers is particularly preferable. When the compatibility of both of the phases to be separated is high, both do not effectively separate in the drying process for evaporating the solvent, and the function as an antiglare layer is reduced.

  The thermoplastic resin and the curable resin precursor (or curable resin) are usually incompatible with each other. When the polymer and the curable resin precursor are incompatible and phase-separated, a plurality of polymers may be used as the polymer. When a plurality of polymers are used, it is sufficient that at least one polymer is incompatible with the resin precursor (or cured resin), and other polymers may be compatible with the resin precursor.

  Further, it may be a combination of two thermoplastic resins that are incompatible with each other and a curable compound (in particular, a monomer or oligomer having a plurality of curable functional groups). Furthermore, from the viewpoint of scratch resistance after curing, one of the incompatible thermoplastic resins (especially both polymers) is involved in the curing of the functional group (participating in the curing of the curable resin precursor). A thermoplastic resin having a functional group).

  When the polymer is composed of a plurality of incompatible polymers and phase-separated, the curable resin precursor is a combination in which at least one of the incompatible polymers is compatible with each other near the processing temperature. Used in. That is, when a plurality of incompatible polymers are constituted by, for example, a first resin and a second resin, the curable resin precursor is compatible with at least either the first resin or the second resin. And preferably compatible with both polymer components. When compatible with both polymer components, at least two phases of a mixture mainly composed of the first resin and the curable resin precursor and a mixture mainly composed of the second resin and the curable resin precursor Phase separate.

  When the compatibility of a plurality of selected polymers is high, the polymers are not effectively separated in the drying process for evaporating the solvent, and the function as an antiglare layer is reduced. Multiple polymer phase separation is easy by preparing a homogeneous solution using good solvents for both components and visually checking whether the remaining solids become cloudy in the process of gradually evaporating the solvent. Can be determined.

  Furthermore, the refractive index of the polymer and the cured or crosslinked resin produced by curing the resin precursor are usually different from each other. Further, the refractive indexes of the plurality of polymers (first resin and second resin) are also different from each other. The difference in refractive index between the polymer and the cured or cross-linked resin and the difference in refractive index between the plurality of polymers (first resin and second resin) are, for example, 0.001 to 0.2, preferably 0.05. About 0.15 may be sufficient.

  The ratio (weight ratio) between the polymer and the curable resin precursor is not particularly limited, and can be selected, for example, from the range of the former / the latter = 5/95 to 95/5, and preferably 5 from the viewpoint of surface hardness. / 95 to about 60/40, more preferably about 10/90 to 50/50, particularly about 10/90 to 40/60.

[Anti-glare film]
The antiglare film of the present invention is composed of at least an antiglare layer, and the thickness of the antiglare layer may be formed of, for example, an antiglare layer alone, but usually further includes a transparent film. An antiglare layer may be formed on one surface of the film.

  For the antiglare layer, conventional additives such as organic or inorganic particles, stabilizers (antioxidants, ultraviolet absorbers, etc.), surfactants, high water-solubility can be used as long as the optical properties of the antiglare layer are not impaired. Molecules, fillers, crosslinking agents, coupling agents, colorants, flame retardants, lubricants, waxes, preservatives, viscosity modifiers, thickeners, leveling agents, antifoaming agents, and the like may be included.

  The thickness of the antiglare layer may be, for example, about 0.3 to 20 μm, preferably about 1 to 15 μm (for example, 1 to 10 μm), and usually about 2 to 10 μm (particularly 3 to 7 μm). In addition, when comprising an anti-glare film only with an anti-glare layer, you may select the thickness of an anti-glare layer from the range of about 1-100 micrometers, for example, Preferably about 3-50 micrometers.

(Transparent film)
Examples of the transparent film (transparent support or substrate sheet) include resin sheets in addition to glass and ceramics. As resin which comprises a transparent film, resin similar to the said glare-proof layer can be used. Preferred transparent films include transparent polymer films such as cellulose derivatives [cellulose triacetate (TAC), cellulose acetate such as cellulose diacetate], polyester resins [polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly Arylate resins], polysulfone resins [polysulfone, polyethersulfone (PES), etc.], polyether ketone resins [polyether ketone (PEK), polyether ether ketone (PEEK), etc.], polycarbonate resins (PC) , Polyolefin resins (polyethylene, polypropylene, etc.), cyclic polyolefin resins (ARTON, ZEONEX, etc.), halogen-containing resins (polyethylene, polypropylene, etc.) Vinylidene chloride), (meth) acrylic resins, styrene-based resin (polystyrene), vinyl acetate or vinyl alcohol resin (polyvinyl alcohol, etc.), and the film formed in the like.

The transparent film may be uniaxially or biaxially stretched, but is preferably optically isotropic. A preferred transparent film is a low birefringence support film. Examples of the optically isotropic transparent film include unstretched films such as polyester (PET, PBT, etc.), cellulose esters, particularly cellulose acetates (cellulose acetate such as cellulose diacetate and cellulose triacetate, cellulose Examples thereof include films formed of cellulose propionate, cellulose acetate C _3-4 organic acid ester such as cellulose acetate butyrate), and the like.

  The thickness of the transparent film having a two-dimensional structure can be selected from a range of, for example, about 5 to 2000 μm, preferably 15 to 1000 μm, and more preferably about 20 to 500 μm.

(Other optical layers)
The antiglare film of the present invention has not only high antiglare properties but also high light scattering properties. In particular, it is possible to increase the scattering intensity in a specific angle range while transmitting and scattering the transmitted light isotropically. Furthermore, the clarity of the transmitted image is high. Therefore, the antiglare film of the present invention has other optical layers (for example, various optical elements disposed in an optical path such as a polarizing plate, a retardation plate, a light guide plate, an antireflection plate, and a low refractive index layer). An optical member may be formed in combination. That is, the antiglare film may be disposed or laminated on at least one optical path surface of the optical element. For example, an anti-glare film may be laminated on at least one surface of the retardation plate, and an anti-glare film may be disposed or laminated on the exit surface of the light guide plate.

  In particular, an antiglare film in which the antiglare layer is provided with scratch resistance can also function as a protective film. Therefore, the antiglare film of the present invention is a laminate (optical member) using an antiglare film instead of at least one of the two protective films of the polarizing plate, that is, at least one of the polarizing plates. It is suitable for use as a laminate (optical member) in which an antiglare film is laminated on the surface. When used as a protective film on both sides of the polarizing plate, glare on the display surface can be prevented and high scratch resistance can be imparted to an optical element (such as a polarizing plate).

  These optical layers may be used instead of the transparent film, and an optical layer may be further laminated in addition to the transparent film.

(Adhesive layer)
In the antiglare film of the present invention, an adhesive layer may be formed on at least a part of the other surface of the transparent film. The antiglare film in which the adhesive layer is formed on the other surface of the transparent film of the antiglare layer can be used as a protective film for various touch panel display devices including smartphones and tablet PCs.

  The adhesive layer is formed of a conventional transparent adhesive. Examples of the pressure-sensitive adhesive include rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, olefin-based pressure-sensitive adhesives (modified olefin-based pressure-sensitive adhesives), and silicone-based pressure-sensitive adhesives.

  Examples of rubber adhesives include combinations of rubber components (natural rubber, synthetic rubber, thermoplastic elastomer, etc.) and tackifiers (terpene resin, rosin resin, petroleum resin, modified olefin resin, etc.). Can be mentioned.

As an acrylic adhesive, the adhesive comprised with the acrylic copolymer which has acrylic acid _C2-10 alkylester as a main component, such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, can be used, for example. Examples of the copolymerizable monomer of the acrylic copolymer include (meth) acrylic monomers [for example, (meth) acrylic acid, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) ) Acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, acrylamide, N-methylolacrylamide, etc.], polymerizable nitrile compound [eg (meth) acrylonitrile etc.], unsaturated dicarboxylic acid or derivative thereof (for example, Maleic anhydride, itaconic acid, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, etc.), aromatic vinyls (eg, styrene, etc.), and the like.

  Examples of the olefin pressure-sensitive adhesive include ethylene- (meth) acrylic acid copolymer, ethylene-2-hydroxyethyl (meth) acrylate copolymer, ethylene-glycidyl (meth) acrylate copolymer, ethylene-vinyl acetate- Examples thereof include (meth) acrylic acid copolymers, ethylene-ethyl (meth) acrylate- (anhydrous) maleic acid copolymers, and partially saponified products of ethylene-vinyl acetate copolymers.

Examples of the silicone-based pressure-sensitive adhesive include a silicone rubber component [monofunctional R ₃ SiO _1/2 (wherein, R represents an alkyl group such as a methyl group, an aryl group such as a phenyl group, etc., the same applies hereinafter). And MQ resin composed of tetrafunctional SiO ₂ ] and a silicone resin component (bifunctional R ₂ SiO alone or bifunctional R ₂ SiO and monofunctional R ₃ SiO _1/2 combined oily or gum) And the like can be used. The silicone rubber component may be cross-linked.

  Among these pressure-sensitive adhesives, silicone pressure-sensitive adhesives are preferable from the viewpoint of optical properties and reworkability.

  The thickness of the pressure-sensitive adhesive layer is, for example, about 1 to 150 μm, preferably about 10 to 100 μm, and more preferably about 20 to 70 μm (especially 25 to 50 μm).

  The adhesive layer may be formed on the entire other surface, or may be formed on a part of the other surface (for example, the peripheral edge). Furthermore, when forming in a peripheral part, in order to improve the handleability for sticking, a frame-shaped member (for example, a plastic sheet is laminated on a peripheral part) is formed in the peripheral part of an anti-glare film, and a frame-shaped member An adhesive layer may be formed.

(Characteristics of antiglare film)
In the antiglare film of the present invention, a large number of fine uneven structures corresponding to the phase separation structure are formed on the surface of the antiglare layer. Therefore, reflection of an outside scene due to surface reflection can be suppressed, and the antiglare property can be improved. Further, the evaluation of the antiglare property can be performed using a gloss meter according to an evaluation by visual reflection of a fluorescent lamp and JlS K7105. The antiglare film (antiglare layer) of the present invention may have a 60 ° gloss of 30 or more, for example, 30 to 80, preferably 40 to 70, more preferably 50 to 60 (particularly 52 to 55). It may be. If the gloss is too small, glare and character blur are likely to occur.

  Furthermore, the evaluation of glare and character blur can be evaluated using a high-definition liquid crystal display device having a resolution of about 200 ppi, and more simply by visual observation using a high-definition smartphone of about 300 ppi. The antiglare film of the present invention can suppress glare even when the antiglare layer is separated from the display surface by 0.05 mm or more (particularly about 0.1 to 0.4 mm) when disposed in a display device having a resolution of 200 ppi. .

  Furthermore, in the antiglare film of the present invention, the optical characteristics that achieve the characteristics of ensuring antiglare properties, reducing glare and avoiding character blur at an optimal level include transmitted image clarity, haze, and total light transmittance. It is preferable to adjust to a specific range.

  When the optical comb having a width of 0.5 mm is used, the transmitted image definition of the antiglare film can be selected from a range of about 70 to 100%, preferably 75 to 100% (for example, 75 to 95%). Preferably, it is about 80 to 100% (particularly 80 to 90%). When the transmitted image definition is too small, the transmitted light is blurred, and when used in a high-definition display device, the outline of the pixel is blurred, and character blur is likely to occur.

  The transmitted image definition is a scale for quantifying blur and distortion of light transmitted through a film. The transmitted image definition is measured through an optical comb that moves the transmitted light from the film, and a value is calculated based on the amount of light in the bright and dark portions of the optical comb. That is, when the film blurs the transmitted light, the image of the slit formed on the optical comb becomes thick, so that the amount of light at the transmissive part is 100% or less, while the light leaks at the non-transmissive part, 0%. That's it. The value C of the transmitted image definition is defined by the following equation from the maximum transmitted light value M of the transparent portion and the minimum transmitted light value m of the opaque portion of the optical comb.

C (%) = [(M−m) / (M + m)] × 100
That is, as the value of C approaches 100%, the image blur due to the antiglare film is smaller [reference: Suga, Mitamura, painting technology, July 1985 issue].

  As a measuring device for measuring the transmitted image definition, Suga Test Instruments Co., Ltd. image clarity measuring instrument ICM-1DP can be used. As the optical comb, an optical comb having a width of 0.125 to 2 mm can be used.

  The haze of the antiglare film of the present invention is, for example, about 10 to 40%, preferably 12 to 35%, more preferably about 15 to 30% (particularly 20 to 30%). When the haze is too high, glare and character blur are likely to occur, and when the haze is too small, the antiglare property is lowered.

  The total light transmittance of the antiglare film of the present invention is, for example, 70 to 100%, preferably 80 to 100%, more preferably 85 to 100% (for example, 85 to 95%), particularly 90 to 100% ( For example, it is about 90 to 99%).

  The haze and the total light transmittance can be measured using a NDH-5000W haze meter manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7105.

  The pencil height (750 g load) of the antiglare film (antiglare layer) of the present invention may be, for example, H or more (particularly 2H or more), for example, H to 4H, preferably about 2H to 3H. May be.

(Production method of anti-glare film)
The antiglare film of the present invention is produced by applying a solution containing a plurality of resin components on a support (especially a transparent film) and forming a phase separation structure by spinodal decomposition accompanying evaporation of the solvent. can get. When the curable resin precursor is included, the antiglare film of the present invention is obtained through a curing step of further curing the curable resin precursor.

  Specifically, in the drying step, a resin composition (particularly a liquid composition or mixed solution such as a uniform solution) composed of a plurality of resin components (particularly a polymer and a curable resin precursor) and a solvent is used. In the process of evaporating or removing the solvent from the liquid phase (or homogeneous solution or coating layer thereof) by drying, etc., phase separation occurs due to spinodal decomposition as the concentration increases, and the interphase distance (pitch or mesh diameter) Can form a relatively regular phase separation structure. The co-continuous phase structure can be produced by setting drying conditions and prescriptions that increase the melt fluidity of the resin composition after the solvent has evaporated.

  More specifically, the wet spinodal decomposition is usually performed by coating a support with a mixed solution or a resin composition (homogeneous solution) containing at least one polymer, at least one curable resin precursor, and a solvent. This can be done by evaporating the solvent from the layer. When a peelable support is used as the support, an antiglare film composed of the antiglare layer alone can be obtained by peeling the antiglare layer from the support, and the non-peelable support is used as the support. By using (preferably a transparent support), an antiglare film having a laminated structure composed of a support and an antiglare layer can be obtained. Furthermore, by increasing the evaporation temperature of the solvent or using a low viscosity component for a part of the resin, a co-continuous phase structure in which the phase separation structure is connected can be produced. The reason why the concavo-convex structure becomes a co-continuous structure is presumed to be that the fluidity of the resin component is not lost even after the solvent evaporates, and the concavo-convex structure is melted and connected by heat.

  In the present invention, in spinodal decomposition, a co-continuous phase structure is formed as the phase separation progresses, and further, when the phase separation progresses and becomes coarse, the continuous phase becomes discontinuous by its surface tension, and the droplet phase structure (Sea-island structure of independent phase such as spherical, true spherical, disk-like or ellipsoidal). Therefore, an intermediate structure between the co-continuous phase structure and the droplet phase structure (phase structure in the process of transition from the co-continuous phase to the droplet phase) can be formed depending on the degree of phase separation. In the present invention, the phase separation structure of the antiglare layer is a sea-island structure (droplet phase structure, or a phase structure in which one phase is independent or isolated) or a bicontinuous phase structure (or network structure) in the initial drying process. It may be an intermediate structure in which a co-continuous phase structure and a droplet phase structure are mixed. With these phase separation structures, fine irregularities can be formed on the surface of the antiglare layer after solvent drying. Furthermore, in the drying process, even after solvent drying, the drying temperature is high enough to ensure fluidity and / or a low-viscosity component is contained as a resin component, so that fine irregularities on the surface are melted. Thus, even if the structure is originally continuous, it can be mutated into a concavo-convex structure with increased continuity.

  In the wet spinodal decomposition, the solvent can be selected according to the type and solubility of the polymer and curable resin precursor, and at least the solid content (a plurality of polymers and curable resin precursors, reaction initiators, other additives) is selected. Any solvent that can be uniformly dissolved may be used. Examples of such solvents include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons ( Cyclohexane etc.), aromatic hydrocarbons (toluene, xylene etc.), halogenated carbons (dichloromethane, dichloroethane etc.), esters (methyl acetate, ethyl acetate, butyl acetate etc.), water, alcohols (ethanol, isopropanol, Butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethylsulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.) Etc. can be exemplified. The solvent may be a mixed solvent.

  As said resin composition (mixed liquid), as a preferable aspect, the said thermoplastic resin, a photocurable compound, a photoinitiator, and the solvent which can dissolve the said thermoplastic resin and a photocurable compound are included. A composition can be used, and as another preferred embodiment, a composition comprising a plurality of incompatible polymers, a photocurable compound, a photopolymerization initiator, and a solvent can be used.

  The concentration of the solute (polymer and curable resin precursor, reaction initiator, other additives) in the mixed solution can be selected within a range where phase separation occurs and a range where casting properties and coating properties are not impaired. It is about 80% by weight, preferably 5 to 60% by weight, more preferably about 15 to 40% by weight (particularly 20 to 40% by weight).

  As the casting or coating method, conventional methods such as spray, roll coater, air knife coater, blade coater, rod coater, reverse coater, bar coater, comma coater, dip squeeze coater, die coater, gravure coater, microgravure coater Examples include coater, silk screen coater method, dip method, spray method, spinner method and the like. Of these methods, the bar coater method and the gravure coater method are widely used.

  Phase casting by spinodal decomposition can be induced by evaporating the solvent after casting or coating the mixed solution. The evaporation of the solvent is preferably performed by heating and drying from the viewpoint that the elongated protrusions can be easily formed on the surface of the antiglare layer. The drying temperature can be selected, for example, from a range of about 30 to 200 ° C. (for example, 40 to 150 ° C.), but a temperature exceeding 80 ° C., for example, 82 to 120 ° C., from the point of easily forming a co-continuous phase structure. The drying can be performed at a temperature of about 85 to 110 ° C., more preferably about 88 to 105 ° C. (especially 90 to 100 ° C.). The drying time is, for example, about 1 to 60 minutes, preferably 1.2 to 50 minutes, more preferably about 1.5 to 30 minutes (particularly 1.8 to 10 minutes). If the drying temperature or time is too low, the heat amount is not sufficiently applied to the resin component, the melt fluidity of the resin component is lowered, and it becomes difficult to form the elongated protrusion. On the other hand, if the drying temperature and time are too high, the elongated protrusion once formed reduces the height by further flow, but the structure is maintained. Therefore, drying temperature and drying time can be used as means for adjusting the antiglare property and slipperiness by changing the height.

  In the present invention, a sufficient amount of heat for melting and flowing the resin component can be imparted by drying at such a relatively high temperature for an appropriate time. Therefore, the elongate convex portions and the co-continuous phase structure can be easily formed by spinodal decomposition accompanied by evaporation of the solvent, and regularity or periodicity can be imparted to the average distance between the domains of the phase separation structure.

  In the curing step, the phase separation structure formed by spinodal decomposition can be immediately fixed by curing the precursor. Curing of the precursor can be performed by heating, light irradiation, or a combination of these methods depending on the type of the curable resin precursor. As long as it has the said phase-separation structure, a heating temperature can be selected from an appropriate range, for example, about 50-150 degreeC, and may be selected from the temperature range similar to the said phase-separation process.

  The light irradiation can be selected according to the type of the photocuring component or the like, and usually ultraviolet rays, electron beams, etc. can be used. A general-purpose exposure source is usually an ultraviolet irradiation device. Note that light irradiation may be performed in an inert gas atmosphere if necessary.

As the light source, for example, in the case of ultraviolet rays, a Deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, a laser light source (light source such as a helium-cadmium laser or an excimer laser) may be used. it can. The amount of irradiation light (irradiation energy) varies depending on the thickness of the coating film, but may be, for example, about 50 to 10,000 mJ / cm ² , preferably 70 to 7000 mJ / cm ² , and more preferably about 100 to 5000 mJ / cm ² .

  Furthermore, when forming an adhesion layer, you may form by apply | coating to the other surface of a transparent film using the conventional method, for example, the above-mentioned casting or application | coating method.

[Display device]
The antiglare film of the present invention has hard coat properties and high antiglare properties. Further, it is possible to improve the light scattering intensity in a specific angle range while transmitting and scattering the transmitted light isotropically. Furthermore, the clarity of the transmitted image is excellent, and there is little character blur on the display surface. Therefore, the antiglare film of the present invention can be used for various display devices such as liquid crystal display (LCD) devices, organic EL display (OLED) devices, plasma displays, display devices with a touch panel, and the like. In particular, the antiglare film of the present invention can be used as a member that does not impair image quality due to glare or blurred characters even in a high-definition display device of 200 ppi or more (particularly 300 ppi or more). Therefore, the antiglare film of the present invention is a device that is often used as a high-definition display device among these display devices, such as a liquid crystal display device (including a liquid crystal display device that is also a display device with a touch panel), organic It can be preferably used for EL display devices (including organic EL devices that are also display devices with a touch panel).

  The liquid crystal display device may be a reflective liquid crystal display device that illuminates a display unit including a liquid crystal cell using external light, and a transmissive liquid crystal display including a backlight unit for illuminating the display unit. It may be a device. In the reflective liquid crystal display device, incident light from outside can be taken in through the display unit, and the transmitted light that has passed through the display unit can be reflected by the reflecting member to illuminate the display unit. In the reflective liquid crystal display device, the antiglare film and the optical member (particularly, a laminate of a polarizing plate and an antiglare film) can be disposed in the optical path ahead of the reflective member. For example, the antiglare film of the present invention may be disposed or laminated between the reflective member and the display unit, on the front surface of the display unit, or the like.

  In a transmissive liquid crystal display device, a backlight unit causes light from a light source (a tubular light source such as a cold cathode tube, a point light source such as a light-emitting diode) to enter from one side and exit from a front exit surface. A light guide plate (for example, a light guide plate having a wedge-shaped cross section) may be provided. If necessary, a prism sheet may be provided on the front side of the light guide plate. In general, a reflection member for reflecting light from the light source toward the emission surface is disposed on the back surface of the light guide plate. In such a transmissive liquid crystal display device, the antiglare film and the optical member can be usually arranged in the optical path ahead from the light source. For example, the antiglare film or the optical member can be disposed or laminated between the light guide plate and the display unit, on the front surface of the display unit, or the like.

  The antiglare film of the present invention is particularly effective for an organic EL display device. The organic EL constitutes a light emitting diode (LED) having a light emitting layer made of an organic compound, and emits light by excitons (excitons) generated by recombination of electrons and holes injected into the organic compound. The light emitting material used for the light emitting layer may be a polymer material using polymer molecules or a low molecular material. In addition, in the organic EL, a light emitting element is configured for each pixel, and this light emitting element is usually a negative electrode such as a metal / electron injection layer / electron transport layer / light emitting layer / hole transport layer / hole injection. Layer / ITO or other positive electrode / glass plate or transparent plastic plate. Further, the organic EL has a heterostructure and confines electrons and holes in separate layers. As a material for each layer, organic substances such as diamine, anthracene, and metal complex are usually used. The thickness of each layer between the electrodes is several nm to several hundred nm, and it is sufficient that the thickness is about 1 μm or less as a whole.

  As a driving method, an active matrix driving method in which an active element such as a TFT (thin film transistor) is arranged and driven in each pixel, or each pixel at the intersection is made to flow by applying current to the stripe electrodes orthogonal to each other at the timing. Any one of the passive matrix driving methods for sequentially driving can be used. As an electrode, ITO etc. are normally used as an anode, and Al, Mg, Ag, Li alloy etc. are used as a cathode. The device structure may be a heterostructure and may be a double heterostructure. As the hole transport material, oxadiazole or triazole may be used. The hole blocking layer may be a phenanthrin derivative. The dopant material may be DCM2 [4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran], coumarin 6, perylene, and the like.

  The reason why the antiglare film of the present invention is useful for organic EL is that the organic EL has high emission intensity of the pixel, and the pixel itself emits light and does not pass through a color filter such as liquid crystal. It can be estimated that this is because there is no directivity and glare is easy. Therefore, in the conventional anti-glare film, when glare is suppressed, the anti-glare property is lowered.

  Further, the antiglare film of the present invention is a liquid crystal display device or organic EL display device (especially organic EL display) in which the pixel arrangement is a pen tile arrangement (an arrangement in which one pixel is composed of two colors of GR or GB and is alternately arranged). The display device can be preferably used because it can suppress glare.

  Furthermore, since the anti-glare film of the present invention can suppress glare even if the anti-glare layer is separated from the display surface, a protective or protective film for an aftermarket for preventing the display device from being damaged (especially an organic EL display device) The protective film can be preferably used. In particular, since the antiglare film of the present invention can suppress glare even if the antiglare layer is disposed at a distance from the display surface, the distance from the display surface (the distance between the display surface and the antiglare layer) is small. It is particularly useful for a protective film that is used at a distance of 0.05 mm or more (particularly about 0.1 to 0.4).

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The antiglare films obtained in Examples and Comparative Examples were evaluated by the following items.

[Size and area of the elongated protrusion]
Based on the reflection laser micrograph, the presence or absence of long convex portions per 1 mm ² was observed, and the average value at any 10 locations was determined for the average diameter of the network of the co-phase structure. Furthermore, in the region of 1 mm ² , the length ratio between the elongated convex part having a branched structure and the other convex part was measured.

  The area of the convex portion was measured using a non-contact surface / layer cross-sectional shape measurement system [“VertScan” manufactured by Ryoka System Co., Ltd.]. In this system, the surface shape can be measured three-dimensionally using optical interference, and the area of the convex portion can be obtained in image processing.

[viscosity]
Using a B type viscometer (“BL type” manufactured by Tokyo Keiki Co., Ltd.), the viscosity at 25 ° C. was measured according to JIS Z8803.

[Haze and total light transmittance]
It measured based on JISK7136 using the haze meter (The Nippon Denshoku Co., Ltd. make, brand name "NDH-5000W").

[Transparent image (map) definition]
Based on JIS K7105, the film sharpness of the optical film and the direction of the comb teeth of the optical comb were measured using a mapping measuring instrument (trade name “ICM-1T” manufactured by Suga Test Instruments Co., Ltd.). The film was placed so that and were parallel to each other and measured. Among the optical combs of the mapping measuring device, the mapping clarity was measured in an optical comb having a width of 0.5 mm.

[60 ° gloss]
In accordance with JIS K7105, evaluation was performed using a gloss meter (“IG-320” manufactured by Horiba, Ltd.).

[Pencil hardness]
Based on JIS K5400, pencil hardness was measured with a load of 750 g.

[Anti-glare]
The anti-glare property was determined by copying a bare fluorescent lamp without a louver onto an anti-glare film, and visually evaluating the glare of the regular reflection light according to the following criteria.

◎: Dazzle is not felt ○: Dazzle is felt slightly ×: Dazzle is felt

[Glitter]
The glare on the display surface is determined by arranging the obtained anti-glare film on a smartphone having an organic EL display with a resolution of 315 ppi (“Galaxy NEXUS” manufactured by Samsung Electronics Co., Ltd.) and visually checking the following criteria: Evaluated according to.

A: Glare is not felt. O: Glare is slightly felt. X: Glare is felt.

[Text blur]
The determination of character blur on the display surface is performed by placing the obtained anti-glare film on a smartphone having an organic EL display with a resolution of 315 ppi (“Galaxy NEXUS” manufactured by Samsung Electronics Co., Ltd.) Evaluation was made according to criteria.

◎: Character blur is not felt ○: Character blur is slightly felt ×: Character blur is felt

Example 1
Acrylic resin having a polymerizable unsaturated group in the side chain [compound in which 3,4-epoxycyclohexenylmethyl acrylate is added to a part of the carboxyl group of (meth) acrylic acid- (meth) acrylic ester copolymer) "Cyclomer P (ACA) 320M" manufactured by Daicel Corporation, solid content 49.6% by weight] 5.65 parts by weight, cellulose acetate propionate (degree of acetylation = 2.5%, degree of propionylation = 46) %, Polystyrene-converted number average molecular weight 75000; “CAP-482-20” manufactured by Eastman Co., Ltd. 1.2 parts by weight, polyfunctional acrylic UV curable compound (“DPHA” manufactured by Daicel Cytec Co., Ltd.), viscosity 5250 mPa · s) 4 parts by weight, acrylic UV curable compound (“PETIA” manufactured by Daicel-Cytec Co., Ltd.), viscosity 1100 mPa s) 2.77 parts by weight of a photoinitiator (BASF Corp. "Irgacure 907") to 0.53 parts by weight were dissolved in methyl ethyl ketone (MEK) 25 parts by weight of 1-butanol 12.15 parts by weight mixed solvent. This solution was cast on a 100 μm thick PET film (“A4300” manufactured by Toyobo Co., Ltd.) using a wire bar # 24, and then left in an oven at 95 ° C. for 2 minutes to evaporate the solvent. A coat layer having a thickness of about 7 μm was formed. Then, the coating layer was irradiated with ultraviolet rays from a high-pressure mercury lamp (manufactured by Eye Graphics) for about 10 seconds, and UV-cured.

When observed with a reflective laser microscope, the entire surface of the coat layer formed a co-continuous phase separation structure as shown in FIG. That is, one continuous net-like elongated convex portion is formed per 1 mm ² , and the ratio of the elongated convex portion having a branched structure among all the convex portions is approximately 100%. In this surface structure, the average diameter of the network in the co-continuous phase structure was about 5 μm, and convex portions were formed in a majority region (95% or more) of the entire surface.

  Moreover, when the sheet | seat obtained on the high-definition organic EL smart phone was affixed, the glare of display was not felt. In addition, there was no reflection of the fluorescent lamp in the room, the anti-glare property was excellent, and there was no blurring of letters.

Example 2
5.65 parts by weight of an acrylic resin having a polymerizable unsaturated group in the side chain [cyclomer P (ACA) 320M], 1.2 parts by weight of cellulose acetate propionate (CAP-482-20), polyfunctional acrylic UV 6 parts by weight of curable compound (DPHA), 0.77 parts by weight of silicone-containing acrylic UV curable compound (“EB1360” manufactured by Daicel-Cytec Co., Ltd., viscosity 2100 mPa · s), photoinitiator (Irgacure 907) 53 parts by weight was dissolved in a mixed solvent of 25 parts by weight of MEK and 12.15 parts by weight of 1-butanol. This solution was cast on a PET film (A4300) having a thickness of 100 μm using a wire bar # 24, and then left in an oven at 90 ° C. for 2 minutes to evaporate the solvent and form a coat layer having a thickness of about 7 μm. Formed. Then, the coating layer was irradiated with ultraviolet rays from a high-pressure mercury lamp (manufactured by Eye Graphics) for about 10 seconds, and UV-cured.

When observed with a reflection laser microscope, as shown in FIG. 3, a bicontinuous phase separation structure having a droplet phase separation structure in part was formed on the surface of the coating layer. That is, one continuous net-like elongated convex portion per 1 mm ² is formed, and the length ratio of the elongated convex portion having a branched structure to other convex portions is the former / the latter = 80 / It was about 20. In this surface structure, the average diameter of the network in the co-continuous phase structure was about 4 μm, and convex portions were formed in a majority region (90% or more) of the entire surface.

  Moreover, when the sheet | seat obtained on the high-definition organic EL smart phone was affixed, the glare of display was not felt. Moreover, there was no reflection of the fluorescent lamp in the room, and the antiglare property was excellent.

Comparative Example 1
A UV-cured coating layer was prepared in exactly the same manner as in Example 1 except that the drying temperature was 70 ° C. When observed with a transmission optical microscope, the coating layer had a droplet-like phase separation structure.

  Also, when the sheet obtained on the high-definition organic EL smartphone was pasted, there was no reflection of the indoor fluorescent lamp, and it was excellent in anti-glare properties and there was no blurring of characters, but the display was glaring. It was.

Comparative Example 2
5.65 parts by weight of an acrylic resin having a polymerizable unsaturated group in the side chain [cyclomer P (ACA) 320M], 1.2 parts by weight of cellulose acetate propionate (CAP-482-20), polyfunctional acrylic UV 6.77 parts by weight of the curable compound (DPHA) and 0.53 parts by weight of the photoinitiator (Irgacure 907) were dissolved in a mixed solvent of 25 parts by weight of MEK and 12.15 parts by weight of 1-butanol. This solution was cast on a PET film (A4300) having a thickness of 100 μm using a wire bar # 24, and then left in an oven at 90 ° C. for 2 minutes to evaporate the solvent and form a coat layer having a thickness of about 7 μm. Formed. Then, the coating layer was irradiated with ultraviolet rays from a high-pressure mercury lamp (manufactured by Eye Graphics) for about 10 seconds, and UV-cured.

  When observed with a reflection laser microscope, the coating layer had a droplet-like phase separation structure as shown in FIG.

  In addition, when the sheet obtained on the high-definition organic EL smartphone was pasted, there was no reflection of indoor fluorescent lamps, and it was excellent in anti-glare properties. Was remarkable.

  Table 1 shows the evaluation results of the antiglare films obtained in the examples and comparative examples.

  As is clear from the results in Table 1, the antiglare films of the examples have excellent antiglare properties and can suppress glare and text blur, whereas the antiglare films of the comparative examples generate glare or text blur. did.

  The antiglare film of the present invention can be used in various display devices such as liquid crystal display (LCD) devices, cathode ray tube display devices, organic or inorganic electroluminescence (EL) displays, field emission displays (FED), and surface electric field displays (SED). It can be used as an antiglare film used in display devices such as rear projection television displays, plasma displays, and touch panel display devices.

  Among these, the antiglare film of the present invention is useful for various displays including PC monitors and televisions, and can achieve both antiglare and glare resistance and character blur suppression for high-definition display devices. It is particularly useful as an antiglare film for displays such as displays for car navigation, smart phones, tablet personal computers (PCs), and display devices with touch panels.

  In particular, a film in which the antiglare layer includes a curable resin precursor is excellent in scratch resistance, and in a display device with extremely high definition (for example, 300 ppi or more), even if the distance from the display surface is separated, Since the optical characteristics can be maintained, it is particularly useful as a protective film (protective film) for the aftermarket of liquid crystal display devices and organic EL display devices.

Claims (13)

An anti-glare film comprising an anti-glare layer on the surface having elongated protrusions formed in accordance with phase separation of a plurality of resin components, wherein the elongated protrusions have a branched structure, and the total An anti-glare film having a length of 200 μm or more and having one or more elongated protrusions per 1 mm ^{2 on} the surface of the anti-glare layer.   The antiglare film according to claim 1, wherein the elongated convex portions form a co-continuous phase structure.   The antiglare film according to claim 1 or 2, wherein a length ratio between the long convex portion having a branched structure and another convex portion is the former / the latter = 100/0 to 50/50.   The transmitted image sharpness measured by an image clarity measuring instrument using an optical comb having a width of 0.5 mm, having a transmitted image clarity of 70 to 100%, a haze of 10 to 40%, and a total light transmittance of 70 to 100%. The anti-glare film as described in 2.   A plurality of resins selected from a styrene resin, a (meth) acrylic resin, an alicyclic olefin resin, a polyester resin, an aliphatic organic acid cellulose ester, and an aromatic organic acid cellulose ester; At least one curability selected from epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, silicone (meth) acrylate, and polyfunctional monomer having at least two polymerizable unsaturated bonds The resin precursor and at least two components of the polymer are phase-separated by spinodal decomposition from a liquid phase, and the curable resin precursor is cured. An anti-glare film according to crab.   The anti-glare film according to claim 5, wherein the curable resin precursor includes a curable resin precursor having a viscosity (25 ° C.) based on JIS Z8803 of 3000 mPa · s or less.   The antiglare film according to any one of claims 1 to 6, which can suppress glare even when the antiglare layer is separated from the display surface by 0.05 mm or more when disposed in a display device having a resolution of 200 ppi.   The antiglare film according to claim 7, wherein the display device is an organic EL panel.   The antiglare film according to any one of claims 1 to 8, further comprising a transparent film, wherein the antiglare layer is formed on one surface of the transparent film.   The antiglare film according to any one of claims 1 to 9, wherein an adhesive layer is formed on at least a part of the other surface of the transparent film.   The antiglare film according to claim 1, which is a protective or protective film disposed on the outermost surface of the organic EL panel.   The manufacturing method of the anti-glare film of Claim 1 including the drying process which apply | coats the solution containing a several resin component on a support body, and forms a phase-separation structure by spinodal decomposition | disassembly accompanying evaporation of a solvent.   The manufacturing method according to claim 12, wherein heating is performed at a temperature exceeding 80 ° C. in the drying step.